EP1867494B1 - Pneus de véhicule à profilé de renfort latéral - Google Patents

Pneus de véhicule à profilé de renfort latéral Download PDF

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Publication number
EP1867494B1
EP1867494B1 EP07107070A EP07107070A EP1867494B1 EP 1867494 B1 EP1867494 B1 EP 1867494B1 EP 07107070 A EP07107070 A EP 07107070A EP 07107070 A EP07107070 A EP 07107070A EP 1867494 B1 EP1867494 B1 EP 1867494B1
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EP
European Patent Office
Prior art keywords
phr
cross
pneumatic vehicle
rubber
reinforcing profile
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Application number
EP07107070A
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German (de)
English (en)
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EP1867494A1 (fr
Inventor
Dr. Carla Recker
Dr. Danka Katrakova
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Continental AG
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Continental AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0025—Compositions of the sidewalls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C17/00—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor
    • B60C17/0009—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor comprising sidewall rubber inserts, e.g. crescent shaped inserts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C2001/0033—Compositions of the sidewall inserts, e.g. for runflat

Definitions

  • the invention relates to pneumatic vehicle tires in radial design with a profiled tread, a multi-layer belt, an inner layer, a carcass executed at least one bead, which is guided around bead cores and bead profiles in bead areas, side walls and at least one each introduced in the region of each side wall, crescent-shaped in cross section Reinforcing profile, which in each case extends over at least a majority of the side wall length and is formed from at least one vulcanized rubber mixture.
  • the tire is provided in the region of its side walls in each case with a mono- or multi-part, approximately crescent-shaped reinforcing profile, which is arranged between the inner layer and the carcass ply and extends below the belt and into the vicinity of the bead areas.
  • the sidewall reinforcing profile, also called self-supporting runflat insert (SSR), of a self-supporting tire in the event of a breakdown is usually made of a hard compound so that the tire can be driven over a certain distance even without air and does not completely fall into place , which causes it to run on the rim and thereby completely destroyed.
  • the mixture of the sidewall reinforcing profile may Do not overheat in the run-down so that the reinforcement profile is not destroyed by reversion of the reinforcement profile.
  • the tire with the sidewall reinforcing profile should differ as little as possible in terms of its driving characteristics and its weight from a conventional tire.
  • EP 1 577 339 A1 rubber blends are proposed for the sidewall reinforcing profile of self-supporting tires having 10 to 100 parts by weight of carbon black and at least 2 parts by weight of crosslinking agent based on 100 parts by weight of rubber, the rubber comprising 10 to 50% by weight of a particular star-shaped, solution-polymerized polybutadiene ,
  • natural rubber and polybutadiene are used in the blend and it is crosslinked with a conventional sulfur accelerator system.
  • the present invention seeks to provide in the event of a breakdown self-supporting pneumatic vehicle tires, which are characterized by an improved run-flat performance, d. H. which can be driven over a longer distance and / or with higher speed in case of a breakdown.
  • the crescent-shaped reinforcing profile can constructively less hard when using the above mixture, z. As thin, can be designed without affecting Pannenlaufadd, thereby the comfort of the tire can be improved at the same time.
  • the urethane or urea bridges can be achieved, on the one hand, in that the mixture contains polymers which have OH groups (lead to urethane bridges) and / or NH groups (lead to urea bridges), each with di- or polyisocyanates as bifunctional crosslinker be networked.
  • the crosslinking of the OH groups leads to urethane bridges and the crosslinking of the NH groups leads to urea bridges.
  • di- or polyisocyanates z.
  • TDI toluene diisocyanate
  • HDI hexemethylene diisocyanate
  • MDI methylene diphenylene diisocyanate
  • bifunctional crosslinkers it is also possible to use all crosslinkers which lead in rubber mixtures with diene rubbers to form urethane or urea bridges. Preference is given to using a nitrosophenol / diisocyanate adduct as the bifunctional crosslinker. Upon addition of heat, these adducts dissociate into p-benzoquinone monooxime and the diisocyanate. The p-benzoquinone monooxime tautomerizes to p-nitrosophenol, which reacts with the polymer to form pendant aminophenol groups. The latter enter into a crosslinking reaction with the diisocyanate to form urethane bonds.
  • nitrosophenol / diisocyanate adduct preferably an adduct of nitrosophenol and methylene bis (4-phenyl isocyanate).
  • This adduct is z. B. under the name NOVOR ® 950 by the company Akrochem Corporation, USA.
  • NOVOR ® 950 by the company Akrochem Corporation, USA.
  • This adduct can be used as the sole crosslinker or in combination with other bifunctional crosslinkers.
  • the rubber mixture of the cross-sectionally crescent-shaped reinforcing profile is vulcanized with the aid of 2 to 12 phr, preferably 3 to 9 phr, of the bifunctional crosslinker. In this way, a network is obtained which ensures an optimum of dynamic durability at high temperatures and high rigidity.
  • phr parts per hundred parts of rubber by weight
  • the dosage of the parts by weight of the individual substances is always based on 100 parts by weight of the total mass of all the rubbers present in the mixture.
  • the rubber mixture of the reinforcing profile is vulcanized additionally and simultaneously with sulfur and at least one vulcanisation accelerator for sulfur vulcanization.
  • the sulfur is preferably used in amounts of 0.2 to 6 phr.
  • the mixtures can be vulcanized in this way in a shorter time window.
  • vulcanization accelerators it is possible to use all accelerators known to the person skilled in the art for sulfur vulcanization, in particular sulfenamide accelerators such as benzothiazyl-2-cyclohexylsulfenamide (CBS). It is also possible to use several vulcanization accelerators simultaneously. In order to further increase the temperature stability of the vulcanizates and to improve the scorch safety (safety against premature scorching), zinc dibenzyldithiocarbamate (ZBEC) is preferably used.
  • ZBEC zinc dibenzyldithiocarbamate
  • Zink-dibenzyldithiocarbamat as accelerator in the sulfur vulcanization particularly many thermally stable S 1 -Netzknoten be achieved and a balanced level of thermally stable network node in combination with thermally and dynamically stable urethane or urea bridges ensures a particularly high runtime performance.
  • Particularly advantageous for the strength of the reinforcing profile is apparent that there are long polymer linker chains adjacent to very short chains and no static distribution over the length of the polymer linker chains as formed in conventional sulfur vulcanization.
  • the rubber mixture for the cross-sectionally crescent-shaped reinforcing profile of the pneumatic vehicle tire preferably contains natural rubber (NR) and / or polybutadiene (BR) as the rubber. If the rubber mixture contains polybutadiene (BR) as diene rubber, these may be both cis-1,4- and 1,2-polybutadiene (both in syndiotactic and atactic form).
  • the rubber mixture for the cross-sectionally crescent-shaped reinforcing profile may also contain other rubbers, in particular diene rubbers, such as. Synthetic polyisoprene (IR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), styrene-isoprene-butadiene terpolymer (SIBR), isoprene-butadiene rubber, styrene-isoprene rubber or styrene-butadiene copolymer (SBR), included.
  • Synthetic polyisoprene IR
  • NBR acrylonitrile-butadiene rubber
  • CR chloroprene rubber
  • SIBR styrene-isoprene-butadiene terpolymer
  • SIBR isoprene-butadiene rubber
  • SBR styrene-isoprene rubber
  • SBR styrene-butad
  • the mixture for the reinforcing profile contains 40 to 90 phr, preferably 50 to 70 phr, hysteresis-poor carbon black having an iodine adsorption number of less than 100 g / kg. It can z.
  • carbon blacks of the type N339, N660, N550 or mixtures of these carbon blacks can be used.
  • the rubber mixture for the cross-sectionally crescent-shaped reinforcing profile may contain other additives customary in the rubber industry, such as, for example, further fillers (eg silica, aluminas, aluminosilicates, aluminum hydroxides, phyllosilicates, chalk, starch, magnesium oxide, titanium dioxide and / or rubber gels), Coupling agents for the connection of the fillers to the rubber, plasticizers, anti-aging agents, activators, waxes, resins and masticating aids.
  • the aggregates are used in conventional amounts.
  • the rubber mixture for the cross-sectionally crescent-shaped reinforcing profile is extruded and placed in the tire blank in the usual way.
  • the blank is then vulcanised.
  • the bead profiles are based on a rubber mixture which is vulcanized with the aid of at least one bifunctional crosslinker to form urethane or urea bridges.
  • Crescent-shaped reinforcing profile and bead profile are preferably based on the same rubber mixture.
  • the bead profiles are exposed to extreme thermal stresses in the event of a breakdown and must be dynamically stiff.
  • the use of identical blends for different tire components offers processing, storage and cost benefits.
  • Fig. 1 a partial cross-section through a pneumatic vehicle tire radial type for passenger cars.
  • Fig. 1 shown cross-section are exemplified the essential components of which the illustrated pneumatic vehicle tire, a profiled tread 1, in the embodiment shown two layers existing belt 2, a single-layered carcass 3, a largely airtight executed inner layer 4, beads 5 with bead cores 6 and bead core profiles (core profiles, apex) 7, as well as side walls 8 and approximately crescent-shaped reinforcing profiles 9.
  • the two layers of the belt 2 consist of embedded in a rubber compound reinforcements made of steel cord, which run parallel to each other within each layer, wherein the Steel cords are oriented one position in a crossing arrangement to the steel cords of the second layer and with the tire circumferential direction each enclose an angle between 15 ° and 30 °.
  • the carcass 3 can also be designed in a conventional and known manner and thus have reinforcing threads of a textile material or steel cord embedded in a rubber compound and extending in the radial direction.
  • the carcass 3 is guided around the bead cores 6 from the inside to the outside, their high passes are in addition to the bead core profiles 7 in the direction belt 2.
  • the reinforcing profiles 9 made of the vulcanized rubber mixture have been positioned on the inner layer 4 during the construction of the tire and are therefore located between the latter and the carcass 3.
  • the thickness of the reinforcing profiles 9 decreases both in the direction of the belt 2 and the direction of the bead 5.
  • Direction belt 2 extends each reinforcing profile 9 to below the edge regions thereof. Over the vast majority of the length of the side wall, each reinforcing profile 9 is made almost constant thick, its thickness at the point of maximum thickness depends on the tire size and the type of tire and can be 5 to 12 mm.
  • reinforcing profiles designed according to the invention can be combined with further reinforcing profiles. Also possible is a different arrangement of the reinforcing profiles than those in Fig. 1 shown, for example, not between inner layer 4 and carcass 3, but between carcass 3 and side wall. 8
  • Table 1 shows comparative and inventive rubber mixtures which can be used for the cross-sectionally crescent-shaped reinforcing profile and optionally the bead profile.
  • the amounts given are parts by weight based on 100 parts by weight of total rubber (phr).
  • the comparative mixtures are marked with V
  • the mixtures according to the invention are marked with E.
  • the amounts of crosslinker, vulcanization accelerator, sulfur and activators were varied. The remaining mixture components remained unchanged.
  • the vulcanizates from the mixtures according to the invention have only a reduced reduction in stiffness with increasing temperature, contrary to the customary behavior, as shown, for example, by the vulcanizates of mixtures 1; the difference between Young's modulus at 250 ° C and that at 150 ° C is reduced. Ie. The vulcanizates are hardly softer with increasing temperature, as occurs in the event of a breakdown. It is thus possible in the event of a breakdown driving over a longer distance and / or at a higher speed.
  • 245/45 R17 tires were constructed having cross-section crescent-shaped reinforcing profiles in the sidewall region of thickness 9.6 mm, the reinforcing profiles being formed from the blends of Table 3 below.
  • the vulcanizate properties were determined according to the test methods listed above (test piece vulcanization: 160 ° C., 20 minutes).
  • the fatigue resistance of the vulcanizates was also determined using a Monsanto Fatigue to Failure Tester (FTF) (cycles to destruction of the sample).
  • FFF Monsanto Fatigue to Failure Tester
  • the mileage of the tire with the mixture 7 (V) as a reinforcing profile was set equal to 100%. Furthermore the comfort behavior of the tires in the usual driving mode (with prescribed air pressure) was evaluated by subjective judgment. The results of the vulcanizate properties and the tire tests are shown in Table 4.
  • Table 4 demonstrates that tires having reinforcement profiles from blends containing a bifunctional crosslinker capable of forming urethane bridges greatly improve the runnability of the tires. At the same time, comfort remains at a high level or even improved. Also, the fatigue resistance of the vulcanizates is significantly improved, which contributes to increased runnability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Tires In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (10)

  1. Pneumatique de véhicule en version radiale avec une bande de roulement profilée (1), une membrure de carcasse radiale multicouches (2), une couche intérieure (4), une carcasse (3) réalisée au moins en monocouche, qui est guidée autour de tringles de talon (6) et de profilés de talon (7) dans des zones de talon (5), des parois latérales (8) et avec au moins chaque fois un profilé de renfort (9) intégré dans la zone de chaque paroi latérale (8), à section transversale en forme de croissant de lune, qui s'étend chaque fois au moins sur une grande partie de la longueur de la paroi latérale et qui est formé d'au moins un mélange de caoutchoucs vulcanisé,
    caractérisé en ce que le mélange de caoutchoucs du profilé de renfort (9) à section transversale en forme de croissant de lune est vulcanisé à l'aide d'au moins un agent réticulant bifonctionnel, sous formation de ponts d'uréthane ou d'urée.
  2. Pneumatique de véhicule selon la revendication 1, caractérisé en ce qu'au moins l'un des agents réticulants bifonctionnels est un produit d'addition nitrosophénol/di-isocyanate.
  3. Pneumatique de véhicule selon la revendication 2, caractérisé en ce qu'au moins l'un des agents réticulants bifonctionnels est un produit d'addition de nitrosophénol et de méthylène-bis-(4-phénylisocyanate).
  4. Pneumatique de véhicule selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que le mélange de caoutchoucs du profilé de renfort (9) à section transversale en forme de croissant de lune est vulcanisé à l'aide de 2 à 12 phr, de préférence de 3 à 9 phr de l'agent réticulant bifonctionnel.
  5. Pneumatique de véhicule selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que le mélange de caoutchoucs du profilé de renfort (9) à section transversale en forme de croissant de lune est vulcanisé en supplément et simultanément avec du soufre et au moins un accélérateur de vulcanisation.
  6. Pneumatique de véhicule selon la revendication 6, caractérisé en ce qu'on met en oeuvre du soufre dans des quantités de 0,2 à 6 phr.
  7. Pneumatique de véhicule selon la revendication 5 u 6 caractérisé en ce qu'en tant qu'accélérateur de vulcanisation, on met en oeuvre du dibenzyldithiocarbamate de zinc (ZBEC).
  8. Pneumatique de véhicule selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que le mélange de caoutchoucs du profilé de renfort (9) à section transversale en forme de croissant de lune contient en tant que caoutchoucs du caoutchouc naturel et/ou du polybutadiène.
  9. Pneumatique de véhicule selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que le mélange de caoutchoucs du profilé de renfort (9) à section transversale en forme de croissant de lune contient de 40 à 90 phr, de préférence de 50 à 70 phr de noir de carbone à faible hysteresis, avec un indice d'adsorption d'iode inférieur à 100 g/kg.
  10. Pneumatique de véhicule selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que les profilés de talon (7) sont basés sur le même mélange de caoutchoucs que le profilé de renfort (9) à section transversale en forme de croissant de lune.
EP07107070A 2006-06-16 2007-04-27 Pneus de véhicule à profilé de renfort latéral Active EP1867494B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102006027867A DE102006027867A1 (de) 2006-06-16 2006-06-16 Fahrzeugreifen mit Seitenwand-Verstärkungsprofil

Publications (2)

Publication Number Publication Date
EP1867494A1 EP1867494A1 (fr) 2007-12-19
EP1867494B1 true EP1867494B1 (fr) 2009-02-18

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AT (1) ATE423021T1 (fr)
DE (2) DE102006027867A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6324815B2 (ja) 2014-05-30 2018-05-16 東洋ゴム工業株式会社 ランフラットタイヤ及びその製造方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57212221A (en) * 1981-06-23 1982-12-27 Nippon Zeon Co Ltd Modification of cis-1,4-polyisoprene rubber
JPH0621187B2 (ja) * 1986-03-24 1994-03-23 日本合成ゴム株式会社 ブタジエン系ゴム組成物
GB8905009D0 (en) * 1989-03-04 1989-04-19 Sumitomo Rubber Ind Method of bonding vulcanisable elastomer compositions to metals
EP1279687A2 (fr) * 2001-07-26 2003-01-29 Sartomer Technology Co., Inc. Polybutadiènes terminées par groupes hydroxyle et formulations de durcissement
DE60239811D1 (de) * 2001-09-05 2011-06-01 Yokohama Rubber Co Ltd Luftreifen mit notlauffähigkeit
US20050049351A1 (en) * 2003-09-02 2005-03-03 D'sidocky Richard Michael Tire with at least one of sidewall insert and/or apex of a rubber composition which contains a high vinyl polybutadiene

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Publication number Publication date
EP1867494A1 (fr) 2007-12-19
ATE423021T1 (de) 2009-03-15
DE502007000440D1 (de) 2009-04-02
DE102006027867A1 (de) 2007-12-20

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